A Thiacalix Basket and Its Anion‐Dependent 2‐D and 3‐D Silver(I) Coordination Polymers via Exo‐Coordination

Thiacalix[4]arene‐ bis ‐1,2;3,4‐crown‐2 (basket or L ) was isolated. Herein we report the first examples of the calix basket complexes. The combination of the basket and silver(I) salts afforded anion‐dependent coordination polymers with different dimensionalities. The AgClO 4 complex 1 , {[Ag 2 ( L )(CH 3 OH)(ClO 4 ) 2 ] · 4CHCl 3 } n has a 2‐D square‐grid network, in which silver(I) atoms link the baskets to form a 1‐D ribbon and these are crosslinked by perchlorate ions. While, the AgPF 6 complex 2 , {[Ag( L )(CH 3 OH)](PF 6 )} n exhibits a multichannel type 3‐D framework with nbo ‐ a topology. Since the basket acts as an ideal exo‐coordinating S 4 ‐platform, the topologies of both products are highly sensitive to the anion coordination.